Paste and powders of acidified metallized azo and triphenylmethane dyes having an average particle size no greater than five microns and production thereof



United States Patent Int. or. (3691, 45/00 U.S. Cl. 8--42 16 Claims ABSTRACT OF THE DISCLOSURE The present invention provides aqueous pastes of chrome dyestuffs consisting of water, an anionic dispersing agent, and a dyestuff selected from the group consisting of sulfonated, sulfocarboxylated and polycarboxylated azo chrome dyestuffs, and sulfonated, sulfocarboxylated and polycarboxylated chrome dyestuffs of the triphenylmethane series which dyestuif is water insoluble in cold water in and acid pH region, but is water soluble in hot water, the paste being acidic so that the dyestuif is insoluble in water at room temperature and their particles having an average size not greater than 5 microns.

This is a continuation-in-part of application Ser. No. 380,079, filed July 2, 1964, and now abandoned.

The present invention concerns improvements in and relating to new pastes and powders containing metallizable dyestuffs.

The chrome dyestuffs used for dyeing or printing of animal fibres and fibres based on super polyamides are usually first dissolved in the form of their alkali metal salts at a pH generally between 6 and 7, and the solutions obtained are acidified before use. However this method has serious disadvantages. During their solution, the chrome dyestuffs are kept for a relatively long time, and frequently at an elevated temperature, in a neutral neutral or weakly alkaline medium and, by its nature, this medium in many cases causes their partial decomposition, which necessarily results in a loss of yield, the actual loss varying in amount with the character of the dyestuffs. Moreover, whatever precautions may be taken, gels or nonhomogeneous coarse precipitates are very often formed on acidification, which bring about lack of uniformity in shade and form deposits on the fibres, the sides of the dyeing apparatus or the rollers of printing machines. In addition the use of calcareous water makes it difficult to obtain correct applications when working in this way.

New compositions of chrome dyestuffs, obtained by grinding these dyestuffs at a pH below 7 with metallic mordants have been described and the interest which these compositions have in dyeing and printing has been shown. But owing to the very fact that the mordant is previously mixed with the dyestuff, such compositions can only be employed for very precise uses and do not offer much flexibility in application, although such flexibility is very often necessary in practice.

According to the present invention aqueous pastes of metallisable dyestuffs are provided containing essentially water, an anionic dispersing agent and a dyestuff selected from the group consisting of the sulphonated, sulphocarboxylated and polycarboxylated metallisable dyestuffs,

3,547,572 Patented Dec. 15, 1970 the pH of said pastes being so adjusted that the dyestulf is practically in the undissolved state at room temperature and their particles having a size or an average size not greater than 5 microns.

The invention also includes powders of metallisable dyestuffs containing essentially an anionic dispersing agent and a dyestuif selected from the group consisting of the sulphonated, sulpho-carboxylated and polycarboxylated metallisable dyestuffs, the particles of the powder having a size or an average size not greater than 5 microns.

It has been found that the compositions of the present invention containing metallisable dyestuffs have great flexibility of application and yet have the same advantages as the compositions described in the above-mentioned patent application. They can be obtained for example in the following manner:

A suphonated, sulphocarboxylated or polycarboxylated, metallisable dyestuif is ground until particles greater than 5 microns in size have practically completely disappeared, by working in aqueous medium at a pH so regulated that the dyestuif is practically undissolved, in the presence of an anionic dispersing agent and in the absence of a metallic mordant, and if desired, the paste so obtained may be dried to a powder for example by spray drying.

With the pastes or powders thus obtained, dyeing of animal fibres and fibres based on superpolyamides can be carried out by the conventional processes of subsequent chroming or chroming in a single bath (processes known as Monochrome or Metachrome). The pastes or powders may be used in dyeing, even with very calcareous water, for dyeing of fibres, threads, fabrics, or felts, for example by means or bath-circulating apparatus. Thus, for example, it is sufficient to make the products into a paste with cold water; the very fine suspension of dyestuif penetrates great thicknesses of carded wool or bobbins of woolen yarn without difliculty. After uniform distribution of the dyestuif in the bulk fibres to be dyed, the dyestuff may then be fixed by progressive heating and metallized by means of salts of polyvalent metals, of which the most generally used are the salts of trivalent or hexavalent chromium. Even without special precautions, the dyeings thus obtained are generally very uniform.

It has already been proposed to apply to animal and synthetic fibres aqueous dispersions of metallizable azo dyestuffs which are insoluble or sparingly soluble in neutral or acid media, but the dyestuffs used for this process are practically insoluble both in the cold and the hot, while the sulphonated, sulphocarboxylated or polycarboxylated dyestuffs used according to the present invention, if they are insoluble in the cold in a particular pH region, have considerable solubility in the hot, and for this reason, are taken up normally on the fibre.

The following examples, in which the parts are parts by weight, are given without the invention being limited thereto.

EXAMPLE 1 parts of Chrome Black TS (Colour Index No. 14,645) in the form of an aqueous paste, are mixed with 19 parts of dinaphthylmethane sodium disulphonate and 1 part of a wetting agent, for example the sodium salt of diheptyl sulphosuccinate. The homogeneous paste 15 then ground to an average particle fineness (which fineness is determined statistically according to known methods of granulometric analysis) of 2 to 3 microns, then subjected to instantaneous drying by spraying in hot air. The powder obtained mixes readily with cold water, giving a microcrystalline suspension which passes rapidly and without residue through filters of cotton cloth or felt. It enables shrunk wool tops of great thicknesses to be dyed in dyeing machines, using bath-circulation, with substantially perfect results, even in a bath of very calcareous water. The original dyestufi dried at pH 6 be used for dyeing tops, fabrics, threads and felts of is soluble at the rate of more than 50 g. per litre in wool or other animal fibres, in a bath circulation appaboiling Water. The dispersed dyestuff, dried at pH 4.5, i'atus. After metallisation for instance with sodium diis insoluble in distilled water at 15 C., in which it dischromate in the presence of formic acid, the dyes have perses giving a very fine suspension which is filterable remarkable fastness to wet tests. without residue in the cold. EXAMPLE 6 EXAMPLE 2 100 parts of carded wool are charged in a compressed The 80 parts of Chrome Black TS in Example 1 are State into a machine for bath circulation dyeing. 6 parts replaced by 80 parts f Chrome Blue-Black R (Colour of the dispersed dyestuif of Example 2 are mixed in 50 Index No. 15,705 The product obtained behaves like parts of water of hydrotimetrie hardness and the that of Example 1. It dyes bobbins of woollen yarn in Suspension is diluted y the addition of 750 Parts of the a circulation apparatus a dark navy blue, according to Same Water and 2 Parts of 100% acetic acid- This y the chroming process known as 2 bath chroming. Even bath is P in the dyeing machine and circulated some when the dyeing is etfected in a bath of calcareous water, minutes- It is then heated to boiling Over a Period of the dyed wool is fast to rubbing and to the potting test. half an hour and p at the boil for half an hour- The dyebath is totally exhausted and the dyestuif is fixed uni- EXAMPLE 3 formly over the whole thickness of the card. The latter 70 parts of Chrome Sky Blue B (Colour Index No. is immediately treated with 2% of sodium dichromate 43,830), in the form of an acid paste insoluble in cold and 2% of formic acid at 100101 C. over a period of water, are treated in a mixer with 29 parts of the dispers- 45 mihhtes- The fihf e is y Uniformly dark navy ing agent used in Example 1 and 1 part of odium lblue shade which is remarkably fast to wet tests, including phoricinolcate. The fluid paste is ground until a sample P g and aeid Overdyeihgdiluted with water leaves no residue on a cotton gabar- Wi h he y ffs f the following le one op rates dine sieve. After instantaneous drying, the dyestuff ena in x pl 1 t0 5- ables dyeing of carded wool rovings to be effected in a The aqueous pastes Containing the dyestutt in the circulation apparatus. After treatment with a mixed bath dissolved State and the anionic dispersing agent, ground of ammonium chromate and chromium oxalate in dilute at least until the disappearance of Particles greater than formic acid, the rovings are dyed a uniform bright blue 5 mierehs in Size, give 0h p yy in hot Powders throughout the thickness of th 11 which mix easily with Water at room temperature. The

EXAMPLE 4 suspensions thus obtained can be used equally for dichromate dyeing in two baths or in printing or dyeing parts of Fast Chrome Green B (Colour Index No. by fouiarding. They may be used whether the fibres are 26,925) as an acid aqueous paste, are treated in a mixer threads, tops, felt or wadding.

Dyestufi Example Dinzotiscd base Coupling component Shade 7 4-sulpho-1-aniin0-2-naphtliol 5-sulpho-1-naphthol Blue. 8 0 H 8-sulpho-1-naphthol. i Greenish blue. 9 l sulpho-l-amino-phenol 1,3-dihydroxy-benzene- Bordeaux. 10... l sulphoG-uitroQ-amiIto-phenol v.do o o Bhiish Bordeaux. 11 6 sulpho 4-chloro-Z-amino-phenol 2,4-dihydroxy-quinolino Bordeaux. 12 G-sulpho-4-nitio-Z-amino-phenol B-Naphthol Brown. 13 6-sulpho-4-nitro-Zamino-phenol 411copentyl-phenol Do. 1t 6-sulpho-4-chloro-2-amino-phonol 8-acetylainino-2-naphthol. Grey. 15 G-sulpho t-iiitro-Z-amino-phenol aeetylacetaniline Yellow. 17... Anthianilie acid 4-sulpho-1phenyl3methyli-pyrazolouo 0. 1B 4-1111enylaininosulphonyl-l-aininobenzone-2,- -diear- 1-phonyl3 methyl-Spyrazolone Do.

boxylic acid. 19 4-5111pho-fi nitro-Z-amino-phciiol B-Naphthol Black. 20 4-sulpho-l-ainino naphthol a-Naphthol Marin 2 o-sulpho-t-chloro amino-phenol"... 4-sulpho-1-nhphthol Violet 2 fi sulplio-i-nitro-l-ainino-phenol 1 phenyl3-mothyl5-pyrazolone Orange 2 4-1lltlO-Q- tlllillO DhQllOl 1-sulph0-1-phenyl-3-methyl-5-pyrazol0no ".0 D0. 2- G-ehloi'o-t-nitro-2-amino-phenol e do 1 1 o Do. 1 4-sulpho-G-nibro-Z-aminO-phonOL 2,4-dlhydroxy-quin0line Red. .1 641itro-4-methyl-2-nmin0-phen0l 4-sulpho-1-phoi1yl-3-methy -5-pyrazolone Rod. 2 3-sulpho-6-chlor0-1-phenyl3-methyl-5- pyrazol0ne Red. 2 8-sulpho1-phenyl-3-methyl-5-pyrazolone Red. 2 l-phenyl-B-methyLfi-pyrazolone 3 4-sulpho-l-phenyl-3 methyl-5-pyrazolone 3 i-sulpho-l-uaphtliol Violet.

with 38 parts of sodium lignin sulphonate and 2 parts of We claim: sulphatcd lauryl alcohol. The homogeneous paste is 1. Aqueous pastes of chrome dyestutls consisting of then ground until particles of dimensions greater than 60 water, an anionic dispersing agent, and a dyestutf selected 2 microns have disappeared, then instantaneously dried. from the group consisting of sulfonated, sulfocarboxyl- The dyestuff thus dispersed mixes readily with cold water, ated and polycarboxylated azo chrome dyestults, and suland can be used either in dichromate dyeing in two baths, fonated, sulfocarboxylated and polycarboxylated chrome or by the Monochrome process, and also in Vigoureux dyestuffs of the triphenylmethane series which dyestuff is printing. In these various methods of use it gives on wool water insoluble in cold water in an acid pH region, but a soft green-blue shade, which is very fast to all wet tests. is water soluble in hot water, the paste being acidic so h etui'nlli'iwatr'iro emera EXAMPLES tatthedys ffsisoube e t omt p ture and their particles having a size not greater than 5 75 parts of Fast Chrome Flavin I (Colour Index No. microns. Z111 aqueous Paste at P are made into a 2. Aqueous pastes as claimed in claim 1 in which the paste in a mixer with 23 parts of the dispersing agent dyestuff is an azo dyestuff. of Example 1, and 2 parts of the sodium salt of diheptyl 3. Powders of chrome dyestuffs consisting of an anionic sulphosuccinate, this paste is finely ground and dried in dispersing agent and a dyestutt selected from the group a spray drier. The dyestutl thus dispersed, without preconsisting of the sulfonated, sulfocarboxylated, and polyvious solution, after simple dispersion in cold water, can carboxylated azo chrome dyestuffs, and the sulfonated,

sulfocarboxylated and polycarboxylated chrome dyestuils of the triphenylmethane series, which dyestuff is water insoluble in cold water in an acid pH region, but is water soluble in hot water, the powders being acidic so that the dyestuff is insoluble at room temperature and their particles having a size not greater than 5 microns.

4. Powders as claimed in claim 3 in which the dyestuff is an azo dyestuff.

5. Process for the preparation of aqueous pastes of chrome dyestuffs which comprises subjecting aqueous pastes of chrome dyestuffs consisting of water, an anionic dispersing agent, and a dyestuff selected from the group consisting of the sulfonated, sulfocarboxylated, and polycarboxylated azo chrome dyestuffs, and the sulfonated, sulfocarboxlylated and polycarboxylated chrome dyestuffs of the triphenylmethane series, which dyestuff is water insoluble in cold water in an acid pH region, but is water soluble in hot water, to grinding until particles of size greater than 5 microns have disappeared, the pH being acidic so that the dyestufi is insoluble at room temperature.

6. Process as claimed in claim 5 in which the dyestuif is an azo dyestuff.

7. Process as claimed in claim 5 in which the paste is spray dried,

8. Process as claimed in claim 7 in which the dyestuif is an azo dyestufi.

9. Aqueous pastes of chrome dyestuffs consisting of water, an anionic dispersing agent, and a dyestuif selected from the group consisting of sulfonated, sulfocarboxylated and polycarboxylated azo chrome dyestuffs, and sulfonated,} sulfocarboxylated and rpolycarbojgylated chrome dyestuffs of the triphenylmethane series which dyestuff is water insoluble in cold water in an acid pH region, butlis water soluble in hot water, the paste'being acidic so that the dyestuff is insoluble in water at room temperature and their particles having an average size not greater than 5 microns.

10.'Aqueous pastes as claimed in claim 9 in which the dyestuff is an azo dyestuff.

11. Powders of chrome dyestuffs consisting of an anionic dispersing agent and a dyestuff selected from the group consisting of the sulfonated, sulfocarboxylated,

and polycarboxylated azo chrome dyestuffs, and the sulfonated, sulfocarboxylated and polycarboxylated chrome dyestuffs of the triphenylmethane series, which dyestutf is water insoluble in cold water in an acid pH region, but is water soluble in hot water, the powders being acidic so that the dyestuff is insoluble at room temperature and their particles having an average size not greater than 5 microns. Y

12. Powders as claimed in claim 11 in which the dyestufi? is an azo dyestuff.

13. Process for the preparation of aqueous pastes of chrome dyestuffs which comprises subjecting aqueous pastes of chrome dyestuffs consisting of water, an anionic dispersing agent, and a dyestuif selected from the group consisting of the sulfonated, sulfocarboxylated and polycarboxylated azo. chrome dyestuffs, and the sulfonated, sulfocarboxylated and polycarboxylated chrome dyestuffs of the triphenylmethane series, which dyestufi is water insoluble in cold water in an acid pH region, but

is water soluble in hot water, to grinding until particles of an average size greater than 5 microns have disappeared, the pH being acidic so that the dyestuff is insoluble at room temperature.

14. Process as claimed in claim 13 in which the dyestufi is an azo dyestuff.

15. Process as Claimed in claim 13 in which the paste is spray dried.

16. Process as claimed in claim 15 in which the dyestuff is an azo dyestufl.

References Cited UNITED STATES PATENTS 2,361,301 10/1944 Libby 8-79X 3,120,508 2/1964 Braun -1 26020'8X 3,419,341 12/1968 Kopp s 42 FOREIGN PATENTS 883,742 12/1961 Great Britain s 79 DONALD LEVY, Primary Examiner US. Cl. XJR. 

